Method of making antiperspirant active compositions having sec chromatogram exhibiting high sec peak 4 intensity

ABSTRACT

A method of making an antiperspirant active composition comprising: heating an aqueous solution containing an aluminum salt having an aluminum to chloride molar ratio of about 0.3:1 to about 3:1, optionally with a buffer agent, at a temperature of about 50° C. to about 95° C. to reflux for a period of time of about 1 hour to about 5 hours to obtain an aluminum salt solution; adding an aqueous solution of an inorganic base to obtain an aluminum salt solution having an OH:Al molar ratio of about 2:1 to about 2.6:1 to obtain a pH adjusted aluminum salt solution having a pH of about 2 to about 5; and optionally adding an aqueous solution containing a zirconium compound to the pH adjusted aluminum salt solution to thereby obtain an aluminum-zirconium salt solution having a molar ratio of aluminum to zirconium of about 5:1 to about 10:1.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is divisional application of application Ser. No.12/446,045, with a 371(c) date of 17 Apr. 2009, which is a nationalstage entry of PCT/US2008/086556, filed on 12 Dec. 2008, which is acontinuation in part of International Application No. PCT/US2007/87145,filed on 12 Dec. 2007, all of which are incorporated herein byreference.

BACKGROUND OF THE INVENTION

Antiperspirant salts, such as aluminum chlorohydrex (also calledaluminum chlorohydrex polymeric salts and abbreviated here as “ACH”) andaluminum zirconium glycine salts (abbreviated here as “ZAG”, “ZAGcomplexes” or “AZG”), are known to contain a variety of polymeric andoligomeric species with molecular weights (MW) of 100-500,000. It hasbeen clinically shown that, in general, the smaller the species, thehigher the efficacy for reducing sweat.

In an attempt to increase the quality and quantity of smaller aluminumand/or zirconium species, a number of efforts have focused on: (1) howto select the components of ACH and ZAG that affect the performance ofthese materials as antiperspirants; and (2) how to manipulate thesecomponents to obtain and/or maintain the presence of smaller types ofthese components. These attempts have included the development ofanalytical techniques to identify the components. Size exclusionchromatography (“SEC”) or gel permeation chromatography (“GPC”) aremethods frequently used for obtaining information on polymerdistribution in antiperspirant salt solutions. With appropriatechromatographic columns, generally five distinctive groups of polymerspecies can be detected in commercial ACH and ZAG complexes appearing ina chromatogram as peaks 1, 2, 3, 4 and a peak known as “5,6”. Peak 1 isthe larger Zr species (greater than 60 Angstroms). Peaks 2 and 3 arelarger aluminum species. Peak 4 is smaller aluminum species (aluminumoligomers, or small aluminum cluster) and has been correlated withenhanced efficacy for both Al and Al/Zr salts. Peak 5, 6 is the smallestaluminum species. Various analytical approaches for characterizing thepeaks of ACH and various types of ZAG actives are found in“Antiperspirant Actives—Enhanced Efficacy Aluminum-Zirconium-Glycine(AZG) Salts” by Dr. Allan H. Rosenberg (Cosmetics and ToiletriesWorldwide, Fondots, D. C. ed., Hartfordshire, UK: Aston PublishingGroup, 1993, pages 252, 254-256).

Attempts to activate antiperspirant salts to produce materials havingimproved efficacy have included developing processes for obtainingcomposition having large amounts of Peak 4 species. None of theseefforts, however, have resulted in an antiperspirant composition havinga composition with little or no Peak 3 and optionally little or no Peak5.

BRIEF SUMMARY OF THE INVENTION

The present invention provides for an antiperspirant active compositioncomprising an aluminum salt having an aluminum to chloride molar ratioof about 0.3:1 to about 3:1, exhibiting a SEC chromatogram having a SECPeak 4 to Peak 3 intensity ratio of at least 7 and a Peak 4 intensitygreater than a Peak 5 intensity in aqueous solution, and optionallyincluding zirconium.

The present invention also provides for a method of making anantiperspirant active composition that exhibits a SEC chromatogramhaving a SEC Peak 4 to Peak 3 intensity ratio of at least 7 and a Peak 4intensity greater than a Peak 5 intensity in aqueous solutioncomprising:

-   I) heating an aqueous solution containing an aluminum salt having an    aluminum to chloride molar ratio of about 0.3:1 to about 3:1,    optionally with a buffer agent, at a temperature of about 50° C. to    about 95° C. to reflux for a period of time of about 1 hour to about    5 hours to obtain an aluminum salt solution;-   II) adding an aqueous solution of an inorganic base to obtain an    aluminum salt solution having an OH:Al molar ratio of about 2:1 to    about 2.6:1 to obtain a pH adjusted aluminum salt solution having a    pH of about 2 to about 5; and-   III) optionally adding an aqueous solution containing a zirconium    compound to the pH adjusted aluminum salt solution to thereby obtain    an aluminum-zirconium salt solution having a molar ratio of aluminum    to zirconium of about 5:1 to about 10:1.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are included to provide furtherunderstanding of the disclosure and are incorporated in and constitute apart of this specification, illustrate embodiments of the disclosureand, together with the description, serve to explain the principles ofthe disclosure.

FIG. 1 illustrates an SEC chromatogram of a prior art antiperspirantactive composition.

FIG. 2 illustrates an SEC chromatogram having exclusive peaks 4 and 5for an inventive product, Example 1, of the present invention.

FIG. 3 illustrates an SEC chromatogram having exclusive peak 4 for aninventive product, Example 2, of the present invention.

FIG. 4 illustrates an SEC chromatogram having exclusive peaks 4 and 5for an inventive product, Example 3, of the present invention.

FIG. 5 illustrates an SEC chromatogram having exclusive peaks 4 and 5for an inventive product, Example 4, of the present invention.

FIG. 6 illustrates an SEC chromatogram having exclusive peak 4 for aninventive product, Example 5, of the present invention.

FIG. 7 illustrates an SEC chromatogram having exclusive peaks 4 and 5for an inventive product, Example 6, of the present invention.

FIG. 8 illustrates an SEC chromatogram of an inventive product from anACH batch scale-up, Example 7, of the present invention.

FIG. 9 illustrates an SEC chromatogram for inventive products, Examples8-10, of the present invention produced within an optimal reactiontemperature range.

FIG. 10 illustrates an SEC chromatogram for inventive products, Examples8, 10, and 11, of the present invention produced within an optimalreaction time range.

FIG. 11 illustrates an SEC chromatogram for an inventive product,Example 12, of the present invention produced within an optimal reactiontime range.

FIG. 12 illustrates an SEC chromatogram for inventive products, Examples13-15, of the present invention produced within an optimalCa(OH)₂:glycine molar ratio range.

FIG. 13 illustrates an SEC chromatogram for inventive products, Examples16 and 17, of the present invention produced at different revolutionsper minute.

FIG. 14 illustrates an SEC chromatogram for inventive products, Examples18 and 19, of the present invention produced within an optimalrevolutions per minute range.

FIG. 15 illustrates an SEC chromatogram for inventive products, Examples20 and 21, of the present invention produced by different methods ofadding Ca(OH)₂.

DETAILED DESCRIPTION OF THE INVENTION

As used throughout, ranges are used as a shorthand for describing eachand every value that is within the range. Any value within the range canbe selected as the terminus of the range.

The present invention is directed to an antiperspirant activecomposition having a high SEC peak 4 in aqueous solution. Thecomposition is obtained by a stepwise procedure to neutralize aluminumchloride in a solution (optionally buffered) using inorganic bases. Insome embodiments, the antiperspirant active compositions obtained bythis stepwise procedure include aluminum salts having an aluminum tochloride molar ratio of about 0.3:1 to about 3:1, the aluminum salt hasa SEC Peak 4 to Peak 3 intensity ratio of at least 7 and a Peak 4intensity greater than a Peak 5 intensity in aqueous solution. Thecomposition may optionally include zirconium.

Optionally, a buffer can be included. Buffers that can be used can bechosen from amino acids, glycine, and betaine. The buffer to aluminummolar ratio in certain embodiments can be about 0.1:1 to about 3:1. Inanother embodiment, the buffer to aluminum molar ratio is about 0.5:1 toabout 2:1. In another embodiment, the buffer to aluminum molar ratio isabout 1:1 to about 1.5:1.

The compositions may be made in a variety of ways involving a stepwiseprocedure to neutralize aluminum chloride in solution (optionallybuffered) using inorganic basic salts. The procedure generally includesthe step of heating an aqueous solution containing an aluminum chloridecompound (optionally with a buffer agent) at a temperature of about 50°C. to about 95° C. to reflux for a period of time of about 1 hour toabout 5 hours. In one such embodiment, an aqueous solution containing analuminum chloride compound is heated at a temperature of about 75° C. toabout 95° C. to reflux for a period of time of about 3 hours to about 4hours. In another such embodiment, an aqueous solution containing analuminum chloride compound and a buffer agent is heated at a temperatureof about 75° C. to about 95° C. to reflux for a period of time of about3 hours to about 4 hours. In one embodiment, the temperature is about85° C.

In some embodiments, the solution has a buffer agent to aluminum molarratio of about 0.1:1 to about 3:1. To adjust the pH of the aluminum saltsolution, an aqueous solution of an inorganic base is added to theheated solution to thereby obtain a pH adjusted aluminum salt solutionhaving a hydroxide to aluminum molar ratio of about 1:1 to about 4:1,and a pH of about 2 to about 5. In one such embodiment, the hydroxide toaluminum molar ratio of about 2:1 to about 3:1. In another suchembodiment, the hydroxide to aluminum molar ratio is about 2.1:1 toabout 2.6:1.

In some embodiments, a zirconium salt may also be added to the pHadjusted aluminum salt solution. In one other such embodiment, the molarratio of Al:Zr is about 5:1 to about 10:1. The antiperspirant activecomposition has a SEC Peak 4 to Peak 3 intensity ratio of at least 7 anda Peak 4 intensity greater than a Peak 5 intensity in aqueous solution.

In one embodiment, an aqueous aluminum chloride salt solution isbuffered with betaine monohydate and held at about 50° C. to about 95°C. to reflux for a period time of about 1 to about 6 hours. To theheated solution, an aqueous solution of an inorganic base is addeddropwise over a period of time of about 1 to about 3 hours whilemaintaining the aluminum-betaine solution at about 50° C. to about 95°C. to reflux. In one such embodiment, the solution has a betaine toaluminum molar ratio of about 1.1. In another such embodiment, thesolution has a betaine to aluminum molar ratio of about 1.25.

In one embodiment, an aqueous solution containing an aluminum chloridecompound is buffered with betaine monohydrate and held at about 75° C.to about 95° C. to reflux for a period of time of about 3 hours to about4 hours. In another such embodiment, an aqueous solution of an inorganicbase is added dropwise over a period of time of about 1 to about 3 hourswhile maintaining the aluminum-betaine solution at about 75° C. to about95° C. to reflux. In another embodiment, an aqueous solution of aninorganic base is added over a period of time in a series of additionswhile maintaining the aluminum-betaine solution at about 75° C. to about95° C. to reflux. In one such embodiment, the inorganic base is added inat least 3 additions. In another such embodiment, the inorganic base isadded in at least 5 additions. In another embodiment, a ZrOCl₂ solutionis added to the pH adjusted aluminum-betaine solution. In one suchembodiment, the molar ratio of Al:Zr is about 8. In another suchembodiment, the molar ratio of Al:Zr is about 7. In one other suchembodiment, the molar ratio of Al:Zr is about 9.

In another embodiment, an aqueous aluminum chloride solution is bufferedwith glycine and held at about 50° C. to about 95° C. to reflux for aperiod time of about 1 to about 6 hours. To the heated solution, anaqueous solution of an inorganic base is added dropwise over a period oftime of about 1 to about 3 hours while maintaining the aluminum-glycinesolution at about 50° C. to about 95° C. to reflux. In one suchembodiment, the solution has an aluminum to glycine molar ratio of about0.4. In another such embodiment, the solution has an aluminum to glycinemolar ratio of about 0.8.

In another embodiment, an aqueous solution containing an aluminumchloride compound is buffered with glycine and held at about 75° C. toabout 95° C. to reflux for a period of time of about 3 hours to about 4hours. In another such embodiment, an aqueous solution of an inorganicbase is added dropwise over a period of time of about 1 to about 3 hourswhile maintaining the aluminum-glycine solution at about 75° C. to about95° C. to reflux. In another embodiment, an aqueous solution of aninorganic base is added over a period of time in a series of additionswhile maintaining the aluminum-glycine solution at about 75° C. to about95° C. to reflux. In one such embodiment, the inorganic base is added inat least 3 additions. In another such embodiment, the inorganic base isadded in at least 5 additions. In one embodiment, the inorganic base iscalcium hydroxide. In one such embodiment, the addition of calciumhydroxide provides an aqueous solution having a Ca(OH)₂:glycine molarratio of about 1.25:1 to about 1:1.

In another embodiment, a ZrOCl₂ solution is added to the pH adjustedaluminum-glycine solution. In one such embodiment, the molar ratio ofAl:Zr is about 8. In another such embodiment, the molar ratio of Al:Zris about 7. In one other such embodiment, the molar ratio of Al:Zr isabout 9.

For the above methods, the aluminum chloride salt and inorganic base maybe obtained from a variety of sources. In one embodiment, the aluminumchloride salt includes aluminum trichloride, aluminum chlorohexahydrateand aluminum dichlorohydrate. In one such embodiment, the aluminumchloride salt is aluminum chlorohexahydrate.

In one embodiment, the inorganic base can be at least one base chosenfrom metal hydroxides, calcium hydroxide, strontium hydroxide, sodiumhydroxide, barium hydroxide, metal oxides, calcium oxide, strontiumoxide, and barium oxide.

The present invention provides for aluminum antiperspirant activecompositions and/or aluminum-zirconium antiperspirant activecompositions having high levels of low molecular weight Al and Zrspecies. As illustrated in FIGS. 2 to 7, the high levels of lowmolecular weight Al and Zr species is reflected in a SEC trace that hasan intense Peak 4, low Peaks 1, 2, 3 and 5. The polymerization of theantiperspirant actives in aqueous solutions and the correspondentgelation process were followed by monitoring the molecular weightprofile of the polyoxohalides in time by SEC. The relative retentiontime (“Kd”) for each of these peaks varies depending on the experimentalconditions, but the peaks remain relative to each other. Data for Tablesin the examples was obtained using an SEC chromatogram using thefollowing parameters: Waters®600 analytical pump and controller,Rheodyne® 7725I injector, Protein-Pak® 125 (Waters) column, Waters 2414Refractive Index Detector. 5.56 mM nitric acid mobile phase, 0.50 ml/minflow rate, 2.0 microliter injection volume. Data was analyzed usingWater® Empower software (Waters Corporation, Milford, Mass.). Theconcentration of the antiperspirant in solution does not affect theretention time in the machine.

The design of modern AP salts aims at actives with high levels of lowmolecular weight Al and Zr species, which is reflected in a SEC tracethat has intense Peak 4 and low Peaks 1, 2, and 3. Throughout thepresent study, the levels of the species corresponding to these peaksare estimated based on the following ratios (or percentages):

${f_{Pi} = {{\frac{Pi}{\sum{Pj}}i} = 1}},2,3,4,{5;{j = 2}},3,4,5$

where f_(Pi) is the fraction of peak i, and Pi or Pj are the intensityof peaks Pi or Pj, respectively. The amount of low molecular weight Alspecies will be correlated with the fraction, f_(P4), or percentage,f_(P4)×100, of SEC-Peak 4. In brief, a preferred antiperspirant saltwould have a very low f_(P1), f_(P2), f_(P3), and/or f_(P5), and a highf_(P4).

In certain embodiments, the ratio of Peak 4 to Peak 3 is at least 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 60,70, 80, 90, 100, or any number up to infinity.

In one embodiment, an aluminum salt and/or aluminum-zirconium salt, inaqueous solution, exhibit a SEC profile wherein the SEC Peak 4 to Peak 3intensity ratio is at least 7. In such embodiments, the percentage ofSEC Peak 4 of a total area of Peaks 1, 2, 3, 4, 5, and 6 in the SECchromatogram is: at least 50%; at least 60%; at least 70%; at least 80%;at least 90%, or 95 to 100%. In another such embodiment, the SEC Peak 4area is 100%.

In another embodiment, the aluminum salt and/or the aluminum-zirconiumsalt, in aqueous solution, exhibits a SEC profile wherein the SEC Peak 4to Peak 3 intensity ratio is at least 7 and exhibits low percentage ofSEC Peak 3. In such embodiments, the composition has the percentage ofSEC Peak 3 area of a total area of Peaks 1, 2, 3, 4, 5, and 6 in the SECchromatogram is: less than about 10%; less than about 5%; less thanabout 2%; less than about 1%; less than about 0.9%; less than about0.8%; less than about 0.7%; less than about 0.6%; of less than about0.5%; less than about 0.4%; less than about 0.3%; less than about 0.2%;or less than about 0.1%. In another such embodiment, the composition hasno SEC Peak 3 area.

In another embodiment, the aluminum salt and/or the aluminum-zirconiumsalt, in aqueous solution, exhibits a SEC profile wherein the SEC Peak 4to Peak 3 intensity ratio is at least 7 and exhibits low percentages ofSEC Peak 5. In such embodiments, the percentage of SEC Peak 5 area of atotal area of Peaks 1, 2, 3, 4, 5, and 6 in the SEC chromatogram is:less than about 30%; less than about 20%; less than about 10%; less thanabout 5%; or less than about 1%. In another such embodiment, thecomposition has no SEC Peak 5 area.

In another embodiment, the aluminum salt and/or the aluminum-zirconiumsalt, in aqueous solution, exhibits a SEC profile wherein the SEC Peak 4to Peak 3 ratio is at least 7, and exhibits a low percentage of SEC Peak1 and a low percentage of SEC Peak 2. In such embodiment, the percentageof SEC Peak 1 area of a total area of Peaks 1, 2, 3, 4, 5, and 6 in theSEC chromatogram is: less than about 10%; a SEC Peak 1 area less thanabout 5%; less than about 2%; less than about 1%; less than about 0.9%;less than about 0.8%; of less than about 0.7%; less than about 0.6%;less than about 0.5%; less than about 0.4%; less than about 0.3%; lessthan about 0.2%; or less than about 0.1%. In another embodiment, thecomplex has no SEC Peak 1 area. In another embodiment, the percentage ofSEC Peak 2 area of a total area of Peaks 1, 2, 3, 4, 5, and 6 in the SECchromatogram is: less than about 10%; less than about 5%; less thanabout 2%; less than about 1%; less than about 0.9%; less than about0.8%; less than about 0.7%; less than about 0.6%; less than about 0.5%;less than about 0.4%; less than about 0.3%; less than about 0.2%; orless than about 0.1%. In another embodiment, the composition has no SECPeak 2 area.

The aluminum antiperspirant active compositions and/oraluminum-zirconium antiperspirant active compositions may be used in avariety of antiperspirant products. If the product is used as a solidpowder, the size of the particles of antiperspirant active of theinvention can be any desired size, and may include conventional sizessuch as in the range of 2 to 100 microns, with selected grades having anaverage particle size of 30-40 microns; finer sized grades having anaverage particle size distribution of 2-10 microns with an average sizeof about 7 microns as made by a suitable dry-grinding method; andmicronized grades having an average particle size of less than about orequal to 2 microns, or less than about or equal to 1.5 microns.

The compositions of this invention may be used to formulateantiperspirants having improved efficacy. Such antiperspirants includesolids such as sticks and creams (creams sometimes being included in theterm “soft solid”), gels, liquids (such as are suitable for roll-onproducts), and aerosols. The forms of these products may be suspensionsor emulsions. These antiperspirant actives can be used as theantiperspirant active in any antiperspirant composition.

Examples of Suitable Formulations

Sticks

-   -   Stick products may be made with conventional gelling agents such        as stearyl alcohol and dibenzylidene sorbitol. A sample        formulation is as follows:    -   40-55% (particularly 45%);    -   cyclomethicone (especially D5 cyclomethicone);    -   20-30% (particularly 21%);    -   stearyl alcohol 7-15% (particularly 10%);    -   talc 15-22% (particularly 22%);    -   antiperspirant active of the invention in particle form; and    -   1-3% (particularly 2%) fragrance.

Roll Ons

-   -   Roll Ons having a sample formulation:    -   45-65% (particularly 55%) cyclomethicone (especially D5        cyclomethicone);    -   0.1-10% (particularly 3%) cyclomethicone/dimethicone copolyol        (such as Dow Corning 2-5185C) 10-25% (particularly 20%);    -   antiperspirant active of the invention in solution form (25-45%        actives on an anhydrous basis in water);    -   5-30% (particularly 20%) water; and    -   1-3% (particularly 2%) fragrance.

Soft Solids

Soft solids may be made with formulations described in U.S. Pat. No.6,682,749. A sample formulation is as follows:

-   -   40-70% (particularly 50%) elastomer in cyclomethicone (KSG-15        from Shin-Etsu);    -   5-15% (particularly 6%) polyethylene (for example, beads having        a density in the range of 0.91-0.98 g/cm³ and an average        particle size in the range of 5-40 microns);    -   10-20% (particularly 15%) C12-15 alkylbenzoate (FINSOLV™ TN from        Finetex);    -   0.1-25%% (particularly 22%) antiperspirant active of the        invention in powder form;    -   1-15% (particularly 5%) dimethicone (particularly with a        viscosity of 100 centistokes); and    -   1-3% (particularly 2%) fragrance.

Gels

Gels may be made with a variety of formulations such as:

-   -   5-50% (particularly 29%) cyclomethicone (particularly D5);    -   0.1-10% (particularly 3%) cyclomethicone/dimethicone copolyol        (such as Dow Corning 2-5185C);    -   0-10% (particularly 5%) hydrogenated polyisobutene 250;    -   0-10% (particularly 5%) C12-15 alkylbenzoate (FINSOLV™ TN from        Finetex);    -   0-10% (particularly 5%) dimethicone (particularly with a        viscosity of 100 centistokes);    -   0.1-25% (particularly 20%) antiperspirant active of the        invention in powder form or 10-25% (particularly 20%) of active        in solution (25-45% actives on an anhydrous basis);    -   5-50% (particularly 30%) water; and    -   1-3% (particularly 2%) fragrance.

Note that in the explanation of the invention, where water is listed itis intended to count the contribution of the water present in theantiperspirant solution as part of the overall water content. Thus,water is sometimes listed as part of the actives solution or sometimeslisted separately.

In one embodiment the refractive indices of the external and internalphases are matched within 0.005 to obtain a clear product.

Other Formulations of Interest

Formulation A

-   -   0.5-2.5% dimethicone copolyol (for example, Dow Corning 2-5185C        (48%));    -   55-65% elastomer in cyclomethicone (for example, DC-9040 from        Dow Corning Corporation (Midland, Mich.) or KSG-15 from        Shin-Etsu Silicones of America (Akron, Ohio));    -   1-10% PPG-3 myristyl ether;    -   10-25% antiperspirant active of the invention;    -   10-25% water; and    -   0.5-1.5% fragrance.

Formulation B

-   -   1.0-3.0% dimethicone copolyol (for example, Dow Corning 2-5185C        (48%))    -   40-60% elastomer in cyclomethicone (for example, DC-9040 from        DowCorning Corporation (Midland, Mich.) or KSG-15 from Shin-Etsu        Silicones of America (Akron, Ohio));    -   1-5% cyclomethicone (in addition to that found in the        elastomer);    -   4-12% PPG-3 myristyl ether;    -   15-30% antiperspirant active of the invention;    -   15-35% water; and    -   0.5-1.5% fragrance.

Formulation C

-   -   1.0-3.0% dimethicone copolyol (for example, Dow Corning 2-5185C        (48%));    -   1-10% hydrogenated polyisobutene (for example, Fancol™. Polyiso        250);    -   40-55% elastomer in cyclomethicone (for example, DC-9040 from        Dow Corning Corporation (Midland, Mich.) or KSG-15 from        Shin-Etsu Silicones of America (Akron, Ohio));    -   3-8% PPG-3 myristyl ether;    -   15-20% antiperspirant active of the invention;    -   20-30% water; and    -   1.0-3.0% fragrance.

Formulation D

-   -   1.0-3.0% dimethicone copolyol (for example, Dow Corning 2-5185C        (48%));    -   40-60% elastomer in cyclomethicone (for example, DC-9040 from        Dow Corning Corporation (Midland, Mich.) or KSG-15 from        Shin-Etsu Silicones of America (Akron, Ohio));    -   3-8% PPG-3 myristyl ether;    -   15-30% antiperspirant active of the invention;    -   15-30% water;    -   0.5-1.5% fragrance; and    -   1-10% diethylhexyl naphthalate

Formulation E

-   -   0.5-2.5% dimethicone copolyol (for example, Dow Corning 2-5185C        (48%));    -   60-70% elastomer in cyclomethicone (for example, DC-9040 from        Dow Corning Corporation (Midland, Mich.) or KSG-15 from        Shin-Etsu Silicones of America (Akron, Ohio));    -   7-10% antiperspirant active of the invention;    -   25-35% water;    -   1-10% methylpropylene diol (MPDiol); and    -   0.5-1.5% fragrance

Formulation F

-   -   1.0-3.0% dimethicone copolyol (for example, Dow Corning 2-5185C        (48%));    -   6-10% hydrogenated polyisobutene (for example, FANCOL™ Polyiso        250);    -   35-45% elastomer in cyclomethicone (for example, DC-9040 from        Dow Corning Corporation (Midland, Mich.) or KSG-15 from        Shin-Etsu Silicones of America (Akron, Ohio));    -   6-10% PPG-3 myristyl ether;    -   40-50% antiperspirant active of the invention as 43% active in        water no additional water; and    -   0.5-1.0% fragrance.

Formulation G

-   -   0.1-0.6% dimethicone copolyol (for example, Dow Corning 2-5185C        (48%));    -   4-7% hydrogenated polyisobutene (for example, FANCOL™ Polyiso        250);    -   40-50% elastomer in cyclomethicone (for example, DC-9040 from        Dow Corning Corporation (Midland, Mich.) or KSG-15 from        Shin-Etsu Silicones of America (Akron, Ohio));    -   4-7% PPG-3 myristyl ether;    -   40-50% antiperspirant active of the invention as 43% active in        water no additional water; and    -   0.5-1.0% fragrance.

Formulation H

-   -   0.5-2.0% dimethicone copolyol (for example, Dow Corning 2-5185C        (48%));    -   1-7% hydrogenated polyisobutene (for example, FANCOL™ Polyiso        250);    -   40-50% elastomer in cyclomethicone (for example, DC-9040 from        Dow Corning Corporation (Midland, Mich.) or KSG-15 from        Shin-Etsu Silicones of America (Akron, Ohio));    -   45-55% antiperspirant active as 43% active of the invention in        water no additional water; and    -   0.5-1.5% fragrance.

Formulation I

-   -   2-7% dimethicone copolyol (for example, Dow Corning 2-5185C        (48%));    -   0.1-1% Oleath-20 1-5% C12-15 alkyl benzoate (FINSOLV™ TN);    -   15-25% elastomer in cyclomethicone (for example, DC-9040 from        Dow Corning Corporation (Midland, Mich.) or KSG-15 from        Shin-Etsu Silicones of America (Akron, Ohio));    -   15-25% antiperspirant active of the present invention;    -   15-30% water; and    -   0.5-1.5% fragrance

The cosmetic composition according to the present invention can bepackaged in conventional containers, using conventional techniques.Where a gel, cream or soft-solid cosmetic composition is produced, thecomposition can be introduced into a dispensing package (for example,conventional packages for gels with glide on applicators, jars where thegel or cream is applied by hand, and newer style packages having a topsurface with pores) as conventionally done in the art. Thereafter, theproduct can be dispensed from the dispensing package as conventionallydone in the art, to deposit the active material, for example, on theskin. For sticks, sprays, aerosols and roll-ons the compositions can beplaced in a conventional types of container (with the inclusion ofpropellants in aerosols). This provides good deposition of the activematerial on the skin.

Compositions of the present invention can be formulated as clear,translucent or opaque products. A desired feature of the presentinvention is that a clear, or transparent, cosmetic composition, (forexample, a clear or transparent deodorant or antiperspirant composition)can be provided. The term clear or transparent according to the presentinvention is intended to connote its usual dictionary definition; thus,a clear liquid or gel antiperspirant composition of the presentinvention allows ready viewing of objects behind it. By contrast, atranslucent composition, although allowing light to pass through, causesthe light to be scattered so that it will be impossible to see clearlyobjects behind the translucent composition. An opaque composition doesnot allow light to pass there through. Within the context of the presentinvention, a gel or stick is deemed to be transparent or clear if themaximum transmittance of light of any wavelength in the range 400-800 nmthrough a sample 1 cm thick is at least 35%, or at least 50%. The gel orliquid is deemed translucent if the maximum transmittance of such lightthrough the sample is between 2% and less than about 35%. A gel orliquid is deemed opaque if the maximum transmittance of light is lessthan about 2%. The transmittance can be measured by placing a sample ofthe aforementioned thickness into a light beam of a spectrophotometerwhose working range includes the visible spectrum, such as a Bausch &Lomb Spectronic 88 Spectrophotometer. As to this definition of clear,see European Patent Application Publication No. 291,334 A2. Thus,according to the present invention, there are differences betweentransparent (clear), translucent and opaque compositions.

EXAMPLES Comparative Examples

A 0.72 M AlCl₃.6H₂O (18 mmol) is held at 90° C. and stirred vigorously.To this solution, a 4 N Ca(OH)₂ (20 mmol) is added dropwise over a 1hour 30 minute period. A ratio of OH:Al of 2.22 is employed in anattempt to prevent the formation of larger unwanted Al species. The pHafter the reaction was 2.36 due to the low OH:Al ratio. The SECchromatogram, illustrated in FIG. 1, exhibits multiple peaks including,SEC-Peak 4, and SEC-Peak 5 indicating multiple Al species are present insolution. At a retention time of approximately 15.5 minutes, SEC-Peak 3is observed due to no buffer (i.e., betaine or glycine) as control.

Also for comparison, 10% solutions are prepared from commerciallyavailable antiperspirants. The solutions are prepared by adding 1 g ofantiperspirant to 9 g of water and mixing. The antiperspirant salts wereReach™ 103, Reach™ 301 from Reheis, and Summit™ Z576 from SummitResearch Labs.

Example 1

A 0.72M AlCl₃.6H₂O (18 mmol) is buffered with 20 mmol betainemonohydrate, held at 90° C., and stirred vigorously. To this solution, a4 N Ca(OH)₂ (20 mmol) is added dropwise over a 1 hour 30 minute period.A ratio of OH:Al of 2.22 is employed in an attempt to prevent theformation of large Al species. The pH after the reaction is 2.56 due thelow OH:Al ratio. As illustrated in FIG. 2, the SEC chromatogram showsexclusively SEC-Peak 4 and SEC-Peak 5, which are known to representactive anti-perspirant species. Substantially no SEC-Peak 3 species isobserved at a retention time of approximately 15.5 minutes.

Example 2

A 0.72M AlCl₃.6H₂O (16.26 mmol) was buffered with 20 mmol anydrousbetaine, held at 90° C., and stirred vigorously. To this solution, a 4 NCa (OH)₂ (20 mmol) was added dropwise over a 2 hour period. A ratio ofOH:Al of 2.46 was employed in an attempt increase the final pH and toreduce SEC-Peak 5 species. Because a higher OH:Al ratio was used, theaddition of the base was extended over a 2 hour period. The pH after thereaction was 4.8. As illustrated in FIG. 3, the SEC chromatogramindicated that the solution contained exclusively SEC-Peak 4antiperspirant active species. Substantially no SEC-Peak 3 species wasobserved at a retention time of approximately 15.5 minutes.

Example 3

A small portion of the solution from Example 2 is taken to determine theeffects of Zr on the peak distribution. ZrOCl₂.8H₂O is added to achievea molar ratio of 8:1, Al:Zr. The pH after adding Zr reduces to 3.7. Asshown in FIG. 4, the SEC chromatogram of this zirconium, aluminumsolution shows two notable features. Firstly, the SEC-Peak 4 remains thepredominate peak, and the SEC-Peak 5 intensity increased to 1%—asexpected by the reduced pH. Secondly, the SEC chromatogram does not showany peaks with retention time of 12.5 minute indicating the absence ofundesirable Zr polymer species. The absence of this SEC-Peak indicatesthat the pure SEC-Peak 4 solution of Example 2 did not promote theaggregation of Zr into larger, less efficacious species. Alsosubstantially no SEC-Peak 3 species is observed at a retention time ofapproximately 15.5 minutes.

Example 4

A 0.5M AlCl₃.6H₂O (25 mmol) is buffered with 31.25 mmol glycine, held at95° C., and stirred vigorously. To this buffered solution, a 1.0 N Ca(OH)₂ (31.25 mmol) is added dropwise over a 1 hour period. A ratio ofOH:Al of 2.5 is employed in an attempt to increase the final pH and toreduce SEC-Peak 5 species. The pH after the reaction is 4.52. The SECchromatogram shown in FIG. 5 exhibits primarily SEC-Peak 4 and a smallerSEC-Peak 5 (520). Substantially no SEC-Peak 3 species is observed at aretention time of approximately 15.5 minutes.

Example 5

A 0.5M AlCl₃.6H₂O (25 mmol) is buffered with 62.5 mmol glycine, held at95° C., and stirred vigorously. To this buffered solution a 1.0 N CA(OH)₂ (31.25 mmol) is added dropwise over a 1 hour period. A ratio ofOH:Al of 2.5 is employed in an attempt to increase the final pH and toreduce the SEC-Peak 5 species. The pH after the reaction is 4.52. TheSEC chromatogram shown in FIG. 6 exhibits exclusively SEC-Peak 4 and noSEC-Peak 5. Substantially no SEC-Peak 3 species is observed at aretention time of approximately 15.5 minutes.

Example 6

A small portion of the solution from Example 5 is taken to determine theeffects of Zr on the peak distribution. ZrOCl₂.8H₂O is added to achievean Al:Zr molar ratio of 8:1. The pH after adding Zr reduces to 3.3. TheSEC chromatogram shown in FIG. 7 exhibits primarily SEC-Peak 4 andsubstantially no SEC-Peak 5 (720). This data indicates that the pureSEC-Peak 4 solution of Example 5 does not promote the aggregation of Zrinto larger, less efficacious species. Also substantially no SEC-Peak 3species is observed at a retention time of approximately 15.5 minutes.

TABLE 1 Comparison of the Examples Comparable Relative Peak DistributionRatio ACH after Reaction (%) Peak 4/ Example OH:Al pH Solution Peak 2Peak 3 Peak 4 Peak 5 Peak 3 Summit ™ Z576 3.1 34.1 40 22.6 1.2 Reach ™103 n/a 10% ACH 63 34 3 0.54 Reach ™ 301 n/a 10% ACH 7 65 12 16 0.18Comparative 2.2 2.36 21% ACH 0 42 42 16 1.0 Example 1 2.2 2.56 21% ACH 00 75 25 ∞ Example 2 2.5 4.8 22% ACH 0 0 100 0 ∞ Example 3 2.5 3.7 22%ACH 0 0 99 1 ∞ Example 4 2.5 4.5  4% ACH 0 0 93 7 ∞ Example 5 2.5 4.52 4% ACH 0 0 100 0 ∞ Example 6 3.32  4% ACH 0 0 98 2 ∞

Large Scale Production of Antiperspirant Active Compositions

Example 7

Process:

-   -   1. Aluminum chloride hexandyrate (3.1055 kg) and anhydrous        glycine (1.1863 kg) were combined in a 316 stainless steel, 25        gallon batch vessel provided with two level hydrofoil blade        agitation using medium (60-80 rpm) agitation. Distilled water        (19.8192 kg) was added to the mixture and the solution was        heated to 85° C. with vigorous (100-125 rpm) agitation.        Temperature control was used to maintain effective temperature        rate increase and target level during the trial. The heating        source was a steam jacket provided with 3 bar/42 psig steam        throughout the trial.    -   2. In a separate reaction vessel, calcium hydroxide (1.1725 kg)        was dissolved in 4.7165 kg of distilled water.    -   3. When the aluminum chloride hexandyrate/glycine solution        reached 85° C., the calcium hydroxide solution was added over a        1 hour 30 minute period. The reaction vessel was vigorously        agitated throughout the addition and care was taken to ensure        that the calcium hydroxide residue did not form at the top of        the vessel.    -   4. After the addition of calcium hydroxide, the solution was        held at 85° C. under vigorous agitation for an additional three        hours. The reaction yielded 30.18 kg (100.4%) of ACH.

Analysis:

SEC analysis showed that the scaled-up synthesis of ACH was successfulin replicating laboratory results: the resultant active solution wasvoid of Peaks 1-3 and contained a very small Peak 5. FIG. 8 shows theSEC profile of the product from the ACH batch scale-up in which Peak 4elutes at 14.5 minutes in both SEC profiles. Visual analysis clearlyindicates that Peaks 1-3 are absent from the ACH solution. There is alsoa strong Peak 4 and a minimal Peak 5. The results of Peak distributionare summarized in Table 2 below.

TABLE 2 Comparison of Peak Distribution of the Scaled-up Batch (ACH) vs.an Activated ACH (Reach ™ 103) Relative Peak Distribution after Reaction(%) Peak 4/ Solution Peak 1 Peak 4 Peak 5 Peak 3 pH Reach ™ 103 61.0035.7 3.3 0.585 4.07 Example 7 0 96.74 3.26 ∞ 3.89

Conclusion:

The result of scaled-up batching in the pilot shows its uniform aluminumspecies under Peak 4 can be obtained in contrast to un-removable largerspecies in current activated ACH (Reach™ 103). The process of thepresent invention can be successfully adopted into any large facilityantiperspirant manufacturers.

Optimal Reaction Parameters for Manufacturing Process

Optimal Reaction Temperature

The reactions for the following Examples 8-10 were all performed with aCa(OH)₂:glycine molar ratio of 1:1 and a OH:Al molar ratio of 2.46:1. Inall three reactions, a 0.65 M AlCl₃.6H₂O (19 mmol) aqueous solution wasbuffered with 23 mmol glycine and heated to 90° C. with stirring. ACa(OH)₂ suspension was added drop-wise by hand to the aqueous aluminumchloride salt solution over 1 hour and 40 minutes, with a total reactiontime of 3.5 to 4 hours. The SEC chromatogram in FIG. 9 illustrates largePeak 4 with negligible Peak 3 for Examples 8-10. There is little to noincrease in Peak 3 formation upon lowering the reaction temperature from90° C. to 75° C. There is only a small increase of 3.9%-6.9% for Peak 5upon lowering the reaction temperatures. A small Peak 5 will add to thelong term stability and efficacy of the active product. Therefore, theoptimal reaction temperature is between 75° C. and 90° C. According tothe SEC peak areas in FIG. 9, the solutions of Examples 8-10 areapproximately comparable to a ˜5% ACH solution.

TABLE 3 Comparison of the Examples (75° C. vs. 90° C.) Relative PeakDistribution Compar- Temper- Basic after Reaction (%) able atureSolution Source Peak 3 Peak 4 Peak 5 ACH (%) (° C.) Example 8 Ca(OH)₂ 092.0 8.0 5.6 75 Example 9 Ca(OH)₂ 0.2 94.8 5.0 5.2 75 Example 10 Ca(OH)₂0 98.9 1.1 4.9 90

Optimal Reaction Time For Synthesis of ACH

The reactions for the following Examples 8, 10, and 11, were allperformed with a Ca(OH)₂:glycine molar ratio of 1:1 and a OH:Al molarratio of 2.46:1. The total reaction time for all three examples was 3-4hours. The SEC chromatogram in FIG. 10 shows only a 0.2% increase inPeak 3 upon lowering the reaction time to 3 hours at 70° C. According tothe SEC peak area, the solutions for Examples 8, 10, and 11 arecomparable to a ˜5% ACH solution. FIG. 10 further shows exclusivelyPeaks 4 and 5 in reactions performed at 75° C. and 90° C. for 4 hours(respectively, Examples 8 and 10).

The reaction for Example 12 was performed with a Ca(OH)₂:glycine molarratio of 1.25:1 and a OH:Al molar ratio of 2.46:1. The SEC chromatogramin FIG. 11 shows favorable results when the reaction was performed usingoptimal parameters and reacted at 75° C. for 3 hours and 30 minutes.FIG. 11 also shows an increase in Peak 3 of 0.8% and an increase of 2.4%for Peak 5 upon lowering the reaction time to 3 hours and 30 minutes at75° C. According to the SEC peak areas in FIG. 11, the solution ofExample 12 is approximately comparable to a ˜5% ACH solution. Therefore,the optimal reaction time is between 3 and 4 hours.

TABLE 4 Comparison of Example Reaction Times Relative Peak DistributionCompar- Temper- Reaction Basic after Reaction (%) able ature TimeSolution Source Peak 3 Peak 4 Peak 5 ACH (%) (° C.) (hrs) Example 8Ca(OH)₂ 0 92.0 8.0 5.6 75 4 Example 10 Ca(OH)₂ 0 98.9 1.1 4.9 90 4Example 11 Ca(OH)₂ 0.2 96.8 3.0 4.7 70 3 Example 12 Ca(OH)₂ 0.8 96.7 2.55.2 75 3.5

Optimal Ca(OH)₂:Glycine Molar Ratio

The reactions for the following Examples 13-15 were all performed usingan OH:Al molar ration of 2.46:1 and were reacted for 2-4 hours. ForExamples 13-15, a 0.235 M AlCl₃.6H₂O (47 mmol) aqueous solution wasbuffered with 23 mmol glycine and heated to 90° C. with stirring. FIG.12 and Table 5 illustrate that the closer the Ca(OH)₂:glycine molarratio is to a 1:1 value, the smaller the relative distributionpercentage of Peak 3. A Ca(OH)₂:glycine molar ratio of 2.5:1 (Example13) produced an increase in Peak 3 by 7.8% compared to the standardreaction (Example 10). A Ca(OH)₂:glycine molar ratio of 2:1 (Example 14)was used, there was a 1.4% increase in Peak 3. When the Ca(OH)₂:glycinemolar ratio was lowered to 1.25:1 (Example 15), there was only a 0.4%increase in Peak 3. Using a Ca(OH)₂:glycine molar ratio of 1.25:1produces a high Peak 4/Peak 3 ratio. Example 12 illustrates that anincrease of only 0.8% in Peak 3 when using a Ca(OH)₂:glycine molar ratioof 1.25:1 at 75° C. Following the optimal reaction parameters, there wasonly a 0.4% increase in Peak 3 compared to Example 15 done at 90° C.Therefore, the optimal Ca(OH)₂:glycine molar ratio is between 1.25:1 and1:1.

TABLE 5 Comparison of Example Ca(OH)₂:Glycine Molar Ratios Relative PeakDistribution Compar- Temper- Basic after Reaction (%) able atureCa(OH)₂: Solution Source Peak 3 Peak 4 Peak 5 ACH (%) (° C.) glycineExample 12 Ca(OH)₂ 0.8 96.7 2.5 5.2 75 1.25:1 Example 13 Ca(OH)₂ 7.892.2 0 4.7 90  2.5:1 Example 14 Ca(OH)₂ 1.4 93.0 5.6 5.0 90   2:1Example 15 Ca(OH)₂ 0.4 94.8 4.8 5.1 90 1.25:1

Optimal Revolutions Per Minute (RPM)

The ACH synthesis of Example 10 at 90° C. over 4 hours used a magneticstir bar for stirring. This method does not provide for a way tospecifically control the revolutions per minute (rpm) of the stirringand results in a product with a great deal of unreacted calciumhydroxide present. The first two reactions were performed at 200 rpm and450 rpm, without covering the top of the reaction flask. This resultedin water loss and turned the solution into a gel which made analysisimpossible. Thus, it is clear that water loss must be minimized whilestirring the reaction to ensure favorable results. FIG. 13 illustratesthe success of reducing water loss and stirring the mixture at a highrpm. Examples 16 and 17 below were performed using an Erlenmeyer flaskfitted with a rubber stopper to help minimize water loss and at 750 rpmand 250 rpm, respectively. Examples 18 and 19 were performed at 600 rpmand 400 rpm, respectively. It is clear that a higher rpm produces a morefavorable product by reducing the formation of Peak 3. FIG. 14illustrates that running the reaction at 500 rpm produced a 0.8%increase in Peak 3 and a slight increase in Peak 5. Therefore, theoptimal revolutions per minute are between 500 and 600 rpm for themethod of this example.

TABLE 6 Comparison of Example Revolutions Per Minute (RPM) Relative PeakDistribution Compar- Basic after Reaction (%) able Solution Source Peak3 Peak 4 Peak 5 ACH (%) RPM Example 16 Ca(OH)₂ 0.2 89.9 9.9 2.7 750Example 17 Ca(OH)₂ 0.6 96.2 3.2 4.0 250 Example 18 Ca(OH)₂ 0.6 94.3 5.15.3 600 Example 19 Ca(OH)₂ 1.2 96.6 2.2 5.2 400

Optimal Method for the Addition of Ca(OH)₂

Simultaneous addition of aluminum chloride, glycine, and calciumhydroxide then mixing and heating yields unfavorable results: 25.5% Peak3 and 16.7 Peak 5 which are poor for the formation of a pure Peak 4complex. Also studied was the addition of a calcium hydroxide power toan aqueous aluminum chloride salt solution once the reaction was at 90°C. This produced increases in Peak 3 by 4.3% to 7.3%, and increases inPeak 5 by 13.3% to 17%. FIG. 15 and Table 7 below illustrate the benefitof using a calcium hydroxide solution compared to a powder. Using acalcium hydroxide solution (Example 20) produced a 1% smaller Peak 3 anda 3.9% smaller Peak 5 compared to using a calcium hydroxide powder(Example 21). The calcium hydroxide in Examples 20 and 21 were added tothe aluminum chloride salt solution 4 times over 1.5 hours. Further, theaddition of a calcium hydroxide suspension initially occurred drop-wiseby hand over 1 hour and 45 minutes. However, Example 10 and FIG. 11illustrates favorable results obtained from adding a calcium hydroxidesolution 5 times over 1 hour and 45 minutes, following all other optimalreaction conditions. Therefore the optimal way to add Ca(OH)₂ is insolution form over several additions.

TABLE 7 Comparison of Ca(OH)₂ solution vs. Ca(OH)₂ powder Relative PeakDistribution Compar- Basic after Reaction (%) able No. of SolutionSource Peak 3 Peak 4 Peak 5 ACH (%) Additions Example 20 Ca(OH)₂ 0.694.7 4.7 4.9 4 additions solution over 1.5 hours Example 21 Ca(OH)₂ 1.689.8 8.6 2.7 4 additions powder over 1.5 hours

1. A method of making an antiperspirant active composition comprising:I) heating an aqueous solution containing an aluminum salt having analuminum to chloride molar ratio of about 0.3:1 to about 3:1, optionallywith a buffer agent, at a temperature of about 50° C. to about 95° C. toreflux for a period of time of about 1 hour to about 5 hours to obtainan aluminum salt solution; II) adding an aqueous solution of aninorganic base to obtain an aluminum salt solution having an OH:Al molarratio of about 2:1 to about 2.6:1 to obtain a pH adjusted aluminum saltsolution having a pH of about 2 to about 5; and III) optionally addingan aqueous solution containing a zirconium compound to the pH adjustedaluminum salt solution to thereby obtain an aluminum-zirconium saltsolution having a molar ratio of aluminum to zirconium of about 5:1 toabout 10:1.
 2. The method of claim 1, wherein the buffer is present in amolar ratio of buffer to aluminum is about 0.1:1 to about 3:1.
 3. Themethod of claim 1, wherein the buffer agent is at least one bufferchosen from an amino acid, glycine, and betaine.
 4. The method of claim1, wherein the inorganic base includes at least one member chosen frommetal hydroxides, calcium hydroxide, strontium hydroxide, sodiumhydroxide, barium hydroxide, metal oxides, calcium oxide, strontiumoxide, and barium oxide.
 5. The method of claim 1, wherein the aluminumchloride compound is chosen from aluminum trichloride, aluminumchlorohexahydrate, and aluminum dichlorohydrate.
 6. The method of claim1, wherein the composition further comprises zirconium.
 7. The method ofclaim 6, wherein the zirconium is ZrOCl₂.8H₂O.
 8. The method of claim 1,wherein the antiperspirant active composition exhibits a Size ExclusionChromatography (SEC) chromatogram having a SEC Peak 4 to Peak 3intensity ratio of at least 7 and a Peak 4 intensity greater than a Peak5 intensity in aqueous solution.
 9. The method of claim 8, wherein theantiperspirant active composition has a SEC Peak 4 area of at least 50%of a total area of Peaks 1, 2, 3, 4, 5, and 6 in the SEC chromatogram.10. The method of claim 14, wherein the antiperspirant activecomposition has a SEC Peak 4 area of 95 to 100% of the total area ofPeaks 1, 2, 3, 4, 5, and 6 in the SEC chromatogram.
 11. The method ofclaim 14, wherein the antiperspirant active composition has a SEC Peak 3area of less than about 10% of the total area of Peaks 1, 2, 3, 4, 5,and 6 in the SEC chromatogram.
 12. The method of claim 14, wherein theantiperspirant active composition has no SEC Peak 3 area.
 13. The methodof claim 14, wherein the antiperspirant active composition has a SECPeak 5 area of less than about 30% of the total area of Peaks 1, 2, 3,4, 5, and
 6. 14. The method of claim 14, wherein the antiperspirantactive composition has no SEC Peak 5 area.
 15. The method of claim 14,wherein the antiperspirant active composition has a SEC Peak 1 area ofless than about 10% and a SEC Peak 2 area of less than about 10% of thetotal area of Peaks 1, 2, 3, 4, 5, and
 6. 16. The method of claim 14,wherein the composition has a SEC Peak 4 area of 95 to 100%, no SEC Peak3 area, and no SEC Peak 5 area of a total area of Peaks 1, 2, 3, 4, 5,and 6 in the SEC chromatogram.